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United States Patent 0 " ICC 2 1 3,049,393 diamine. The nitro derivative obtained is reduced to beta aminoethyl p-phenylene diamine which is thereafter - NITRO PHENYLENEDIAMINE COMPOSITIONS AND METHOD FOR DYEING ANIMAL FIBERS acetylated. The triacetyl derivative obtained is nitrated, John Robert Seemuller, Maisons-La?itte, France, assignor to Société Anonyme (lite: L’Oreal, Paris, France, a cor poration of France a 3,049,393 Patented Aug. 14, 1962 and then deacetylated in order to obtain the desired com 5 pound. The steps of this synthesis are represented below. No Drawing. Filed Apr. 12, 1961, Ser. No. 102,102 Claims priority, application France Nov. 29, 1955 11 Claims. (Cl. 8—10) 01 NH-oHr-cHr-NH, I The present invention relates to new nitro-aromatic compounds and their use in dyeing, particularly for dye ing animal ?bres and more especially dyeing live hair. Many dyestuffs of the type containing an aromatic nu cleus having one or more substituted or unsubstituted amino groups and/or a number of nitro groups have been 15 N0, NO: I () (n> employed for dyeing animal ?bres. The conditions which must be satis?ed in dyeing live hair, which include dyeing at a temperature which can be withstood by the subject, minimum toxicity, and effective application to grey, white or bleached hair, considerably limit the number of dyes 20 —. which can be so used. There have already been described and proposed for NH-O O~CH1 such a use nitro aromatic diamines such as, for example nitro-p-phenylenediamines in which the amino group meta to the nitro group, is mono-substituted by a mono- or poly-hydroxy-alkyl group. However, compounds of this (III) 25 (IV) /C O-GH; N type in which the substituent on the amino group‘ is a NH-CHz-CHz-NHI hydroxy methyl radical, have inadequate stability even when the hydroxyl group is esteri?ed with an inorganic acid. The same holds true when the hydroxy-alkyl radical 30 N0: is heavier, for example, hydroxyethyl or hydroxyiso propyl. Introducing hydroxyl groups in these compounds, as well as esterifying these groups with an inorganic poly N0’ NH-C O—OH; NH; (V) (VI) basic acid aims at increasing the Water-solubility of the 35 The method of operation followed and the character istics of the compounds obtained are as follows: dyes, which are otherwise sparingly soluble. The Compound II is prepared by the process of I. P. F. It is an object of this invention to provide stable nitro Fourneau and Madame Y. de Lestrange (Bull. Soc. Chim. phenylene diamine compounds which are particularly suit 1947, page 834). able for dyeing animal ?bres, and more especially live REDUCTION OF THE COMPOUND II TO THE hair, at moderate temperatures. It is a further object to 40 provide compositions containing such compounds. COMPOUND III The nitro, ortho and para-phenylenediamine, in which 300 g. of iron powder are introduced into 1200 ml. of water to which 10 ml. of glacial acetic acid have been added and the mixture is heated to 85—90° C. 181 g. (1 the nitro group is in a meta position to one of the amino groups, and in which the amino group remote from the 45 mol.) of Compound II are then gradually added, the tem nitro is a group which has the general formula perature being maintained at 90° C. while 55 m]. of acetic acid are added in the course of the reduction. The in which R1, R2 and R3 each represent an atom of hydro reaction is complete within half an hour. The reaction gen or an alkyl radical having from one to 3 atoms of product is made alkaline with 4 g. of sodium carbonate carbon, m represents an integer between 2 and 4 and n 50 and ?ltered hot. is equal to 0 or 1. It is unnecessary to isolate Compound III in order to According to a further feature of the invention a com effect the acetylation. position for application to the hair for dyeing same com ACE'I‘YLATION OF THE COMPOUND III TO THE prises an alkaline solution of a compound as just de?ned. COMPOUND IV According to a still further feature of the invention a 55 Immediately after the ?ltration, 425 g. of acetic an method of dyeing animal ?bres and more particularly live hydride are added to the ?ltrate at 90° C. with vigorous hair comprises applying thereto an alkaline solution of a stirring and the mixture is heated for 1 hour at 80-90° C. compound as just de?ned. After cooling, 500 g. of crushed ice are added and the The following examples will serve to illustrate the in vention but are not to be regarded as limiting it in any 60 mixture is neutralized with 550 ml. of 40% sodium hy droxide solution, care being taken that the temperature way: does not rise above 7° C. The triacetyl derivative IV EXAMPLE 1 is allowed to crystallize, ?ltered and dried at 65~70° C. It melts at 191° C. and the yield is 94%. After re I-Amino-Z-Nitro-lI-?-Aminoethylamino-Benzene NH—CH;CHzNHg 65 crystallization, the melting point is 195-l96° C. Analysis: Element Calculated Found percent ' I percent’; . N0: in. p-Nitrochlorobenzene is ?rst condensed with ethylene ....................................... .. 70 H ....................................... -- 60.64 ' 60.24 6.85 7.11 15.16 15.15 3,049,393 4 ‘ the hydrochloride, which melts at 233—235° C. Yield: NITRATION OF‘ THE COMPOUND IV 60%. 84 g. of the Compound IV are dissolved in 500 ml. of While the amine of Formula VIH hydrates readily, the concentrated sulphuric acid (66° Bé.) and the nitration hydrochloride prepared as indicated above keeps well. is effected at 15° C. by pouring in a sulphuric nitric acid mixture consisting of 66 g. of nitric acid having a density 5 It is dissolved in 800 ml. of water, neutralized with 40% aqueous sodium hydroxide solution and the precipitated of 1.38 and 66 g. of concentrated sulphuric acid, the tem product is ?ltered and dried in a desiccator for 3 days. perature being maintained between 20° and 25°C. for The free amine thus prepared melts at 84-85” C. Yield: 41/: hours. The product is poured on to crushed ice and 80%. neutralized with 40% aqueous sodium hydroxide solu Controlled reduction.~—0.l mol. of the Compound VIII tion, care beaing taken that the temperature does not rise 10 is brought into suspension in 450 ml. of ethyl alcohol above 40° C. The reaction mixture is extracted with containing from 8% to 9% of NH3 added. Hydrogen ethyl acetate. The extract is then distilled to drive off sulphide gas is then bubbled therethrough. Dissolution the ethyl acetate and the residue is recrystallized from of the Compound VIII is complete within 15 minutes absolute alcohol. 35 g. of the Compound V are thus obtained in the 15 and the solution turns gradually orange, red and dark brown. The stream of gas is bubbled through for 6 form of lemon-yellow needles melting at 207-208" C. hours at a temperature of between 30-40“ C. DEACETYLATION OF THE COMPOUND V The alco holic solution is then evaporated to dryness under reduced The Compound V is re?uxed for an hour and a half pressure. with 200 ml. of 50% aqueous sulphuric acid. After 20 The residue is dissolved in 7% hot aqueous hydro cooling, 600 ml. of ethyl alcohol are added. The mix chloric acid. The sulphur which has precipitated is ture is left overnight in a refrigerator, and the crystals ?ltered. The hydrochloride is then neutralized with 40% formed are then ?ltered. The dark-colored viscous resi aqueous sodium hydroxide solution. The base precipi due is warmed, ?ltered through bone-black and returned tates upon cooling. On successive recrystallizations into the refrigerator. A further quantity of crystals is 25 from water in the presence of bone-black, red ?akes melt recovered. The sulphate of the compound of Formula ing at 135—136° C. are obtained. Yield: 50%. VI is thus obtained in the form of yellow crystals which The base, Formula IX, is dried in a desiccator. decompose at 185° C. The free base is very hygroscopic Dyeing.—A 1% solution of the Compound IX is pre and it is preferred to use the sulphate. pared and made weakly alkaline, and this solution is Dyeing.—A 2% aqueous solution of 1-amino-2-nitro applied in the cold to live hair. A golden shade is ob 4-;3~aminoethylamino-benzene sulphate is prepared and 30 tained, which is brighter than that obtained with nitro-o made alkaline by adding a base, for example ammonia. phenylenediamine. This solution is applied in the cold to live hair or sim ilar ?bres, and a beautiful dark violet shade is obtained. EXAMPLE 3 1-Amin0-2-Nitr0-4-N-A cetamido-Amino-Benzene The addition of hydrogen peroxide does not shift the 35 shade. NH-C Hr-C O-NH: EXAMPLE 2 1-Nitr0-3-Amin0-4-B-Aminoethylamino-Benzene .' NO’ This product is obtained by condensation of ethylene 40 diamine with 1,3-dinitro-4-chlorobenzene, which gives, NH: 1,3-dinitro-4-l3-aminoethylamino-benzene, which in turn This compound is prepared by condensing chloroacet gives the required compound when reduced with sodium hydrosulphide. amide with nitro-p-phenylene diamine in accordance with The steps of the synthesis are represented in the fol- 45 the following scheme: lowing: NH; NH-CH:—G O—NH2 Cl ———r N0: 60 N 0, NHz (X) N0: (VII) N0! NH: (XI) Line of proceeding-Into a round ?ask equipped with NO: NH: 55 a mercury-sealed stirrer is introduced 0.8 mol. of nitro p-phenylene diamine. 60 g. of calcium carbonate, 1 litre of hot water and 0.8 mol.+10% of chloroacetamide are added, the carbon dioxide evolved being collected in order to check the progress of the reaction. The re action mixture is re?uxed for 31/2 hours, and is then ?l N 0: (VIII) N03 (IX) tered hot. The resulting product is allowed to crystallize and is washed again with water. A compound melting at 183° C. is obtained. Yield: 60%. Condensation.-Into a round ?ask equipped with a re ?ux condenser are introduced 150 g. of 97% pure ethyl 65 ‘ After crystallization from water, a violet powder melt ene diamine and 9.5 g. of anhydrous cupric chloride. 0.6 mg at 190° C. and pointing to Formula X1 is obtained. Analysis: mol. Compound VII is gradually added. The tempera~ ture rises to 85° C. and is maintained at this level for half an hour with heating. The solution is then poured into 2 litres of ice-cooled water. The precipitate formed 70 is ?ltered, dissolved in 2 litres of water, ?ltered again, pasted with a little water and then ?ltered again. After the last ?ltering, the precipitate is dissolved in 300 ml. of boiling ethyl alcohol and ?ltered, and 10% aqueous hydrochloric acid is added to the ?ltrate to form 75 Element Calculated percent ' Found percent. g....................................... ._ 45. 71 4.76 45.64 4.87 N 26.66 26.89 - Dyeing.—A 1% solution of 1-amino-2-nitro-4-N 3,049,393 5 6 acetarnidoaminobenzene is prepared and made weakly alkaline with ammonia. This solution imparts a red tint Dyeing test.—A dyeing test carried out under the same conditions as with the preceding composition yielded com to live or dead hair. parable results. The shade obtained is not sensitive oxidizing agents such as for example, hydrogen peroxide. EXAMPLE 4 5 1-N(Bem-Diethylamino-Ei/zyl) Nirr0-3-Diami1101,4-Bcnzene EXAMPLE 6 1-N[(Beta-Diezhylamino-Ethyl) (Methyl)] Nitro-3 Dmmmo'l??enzme (32H5 CQHS NIr-oHQoIhN _ CH3~N—CH2CH2N | 10 \ C2Ha C2115 —-N0: No, l 15 NH; 11111, This product is prepared from nitroparaphenylene- This?omposilion is Prepared from I-NQmethYU-HitI‘O diamine, by condensation with the hydrochloride of beta- 3-dl?mlno-L4-Penlene by Cond?nsatlon W_lth hydrochlo diethyl amino-chloro-ethane, in the presence of calcium ride of beta-dlethyl-amino-chlofo'cthane 1? an aqueous carbonate, in an aqueous medium, by re?uxing. 20 medium in the presence of an excess of calcium carbonate A mixture of 15.3 grams (0.1 mole) of nitropara~ phenylenediamine, and 10 grams (0.1 mole) of calcium by re?llXfIlg _IT1 a mlxtllfe 0f 3-35 grams (0-05 H1016) 0f l-N(melhyl) carbonate in 100 cc. of water, is heated to boiling for a n1tr°—3 diamlno-L4-benlene, 7 grams (O-07 mole) 0f__¢a1 period of 35 minutes, 19 grams (0'11 mole) of hydro. cium carbonate and 85 cc. of water, heated to boiling, chloride of beta-diethylamino-chloro-ethane dissolved in 25 there is_ added drop by drop, Over a Perlod 0f 35 minutes, 50 cc_ of Water, is added drop by drop a solution of 12.66 grams (0.07 mole) of the hydrochlo After the carbon dioxide has ceased to be released, it ride of beti1-diethyl-amino‘clllofp'ethane in 35 cc- of is ?ltered and the excess of calcium carbonate is elim- Water, to release the ¢_aTb_°n ‘lloxlde' inated. After cooling, the hydrochloride of 1-N(beta- _ Aftfir the Pal'boll dloxlfie 15 P0 longer ‘belng releatsed diethylaminoethyl) nitro-3-diamino_Lmbenzene precipl; 30 the mixture is ?ltered at 1ts boiling temperature to elim tates out in the-form of brownish red crystals. Yield; inate the excess of calcium carbonate. Then, after cool 7()%_ This hydrochloride when remwstalhzed from methanol, ing, the ?ltrate is alkalized by adding ammonia. The liberated base is extracted with ether and isolated in the melts with decomposition at 180—182° C. usual manner in the form of an'oil- Analysis: 35 Element Theory Found _ This base is then transformed into a hydrochloride by passing gaseous hydrochloric acid into the methanol solu tion. The precipitated hydrochloride is then ?ltered and vacuum dried. There is thus obtained a yield of 60% di 0 ....................................... __ 49. 91 49.19419. 45 N62355- £1111: ----------------------- __________________________ n ' ' chlorhydride of l-N[(beta-diethyl-amino-ethyl) (methyl)] 40 nitro-3-diamino-1,4-benzene which, when recrystallized ' in methanol, melts with decomposition at 162-163" C. Dyeing tesz‘.-—An aqueous, 1% solution of this com- Analysis: position brought to pH 7 by the addition of ammonia was applied cold to white living hair and left in contact 45 therewith for ?ve minutes. The hair was dyed a very Element Theory deep red violine shade. Found 46.01 EXAMPLE 5 1-N(Beta-Dimethylamin0—Ethyl) Nitr0-3-Diamin0- 46. 20-45. 18 7. 07 7. 06-7. 16 111.51 16.64-16.85 50 1,4-Benzene Dyeing test.—A 2% aqueous solution of this composi CH3 tion, brought to pH 7 by addition of ammonia, applied cold to white hair and left in contact therewith for 15 minutes, dyed the hair an intense violine shade. / NATCHiCH’N OH“ 55 _N02 EXAMPLE 7 1-N(Beta-Diethylaminc-Ethyl) Nitro-4-Diamin0 LIZ-Benzene NH; oil-I5 Under the same conditions as for the composition of 60 NIL-OHQCHQN/ l-N(beta-diethylamino-ethyl) nitro - 3 - diamino-1,4-ben- C H zene, by condensation of hydrochloride of beta-dimethylamino-chloroethane on nitroparaphenylenediamine a yield of 50% chlorhydratc of l-N(beta-dimethylamino-ethyl) nitro-3-diamino-1,4-benzene is obtained which, when recrystallized with methanol melts with decomposition at 2 5 205-208° C. r ‘’ , ‘N112 I N01 _ Analysis: Element Theory Found _ , _ _ , _ Th1s compositlon is prepared by reducing with sodium sul?de in a hydro-alcohol medium (beta-diethylamino 70 ethyl) dinitro-2,4-aniline. The latter product is obtained in a known manner by condensing dinitro 2,4-chloroben zene with N-N-diethyl-ethylenediamine. 42:23 “692E332; To a solution of 42.5 grams (0.15 mole) of beta 2150 21-43'21-56 diethyl-amino-ethyl-dinitro-Z,4-aniline in 600 cc. in 95% 75 ethyl alcohol at a temperature of 95° there is added, drop 3,049,393 by drop, a solution of 21.5 grams (0.385 mole) of sodium EXAMPLE 9 sul?de in 600 cc. of ethyl alcohol at 95° and 48 cc. of 1-N[ (Befa-Diethylaminoethyl) (Ethyl) ] Nitr0-3 - water over a period of an hour and a half. Diamin0-1,4-Benzene The alcohol is evaporated under a vacuum and the sul ?de is dissolved in 209 cc. of 10% hydrochloric acid. The solution is ?ltered and 42.5 cc. of 20% ammonia is added at a temperature below 20° C. solution obtained is about 7. The pH of the The monochloride precipitates and when recrystallized from alcohol melts with decomposition at 210° C. Yield: 10 80%. NO: IllH: By dissolving this hydrochloride and alkalizing it with sodium hydroxide in an aqueous solution, the correspond ing base may be obtained after cooling, which base when recrystallized from benzene, melts at 62° C. This product is prepared from 1-N(ethyl) nitro-3-di amino-1,4-benzene by condensation with beta-diethyl amino-chloro-ethane. Analysis: In a mixture of 9.05 grams (0.05 mole) of 1-N(ethyl) nitro-3-diamino-1,4-benzene, 4 grams (0.04 mole) of calcium carbonate and 80 cc. of water, there is added, as , Calculated at Element CIZHMN‘O2 Found 20 it boils, 13.32 grams (0.077 mole) of beta-diethylamino chloro-ethane in 35 cc. of water (duration of addition: C. ....................................... .. H _______________________________________ -. 57. 15 7. 94 57. 38-57. 15 8. 01-7. 87 N _______________________________________ __ 22. 21 21.80-21.85 2 hours). The mixture is cooled and extracted with methyliso butyl-ketone to remove any 1-N(ethyl) nitro-3-diamino 25 1,4-benzene which has not been transformed. The mother liquors are then alkalized by using 40% sodium hydroxide. Extraction by ether follows, and after conventional treat ride of this composition was brought to pH 7 by adding ment a violet oil is obtained. This product when puri?ed ammonia, and applied cold to grey hair, and after a con by passing its methyl alcohol solution over alumina, al tact of 15 minutes produced a bright yellow shade. 30 ways yields an oil after evaporation of the methyl alco hol. Yield: 75%. EXAMPLE 8 Analysis: Dyeing test.—-An aqueous solution of 1% hydrochlo 1-N( Gamma-Diethylamino-Propyl) Nitro-3-D iam ino Element 1,4-Benzen‘e Theory Found 35 0 ....................................... .H _______________________________________ __ N 40 60. 00 8.57 20. 00 60-55-60. 32 9.00-9.58 19. 52-19. 69 An aqueous 1% solution of 1-N[(beta-diethylamino ethyl) (ethyl)] nitro-3-diamino-1,4-benzene, adjusted to a pH of 7, is applied cold to white hair and allowed to NO: remain in contact therewith for a period of 15 minutes and produces a rose-beige tint. NB: This application is a continuation in part of applica This product is prepared from nitroparaphenylene diamine by condensation with gamma-diethyl-amino 45 tion Serial No. 624,227, ?led November 26, 1956, now abandoned. chloro-propane in an aqueous medium, by re?uxing. A mixture of 11 grams (0.072 mole) of nitropara phenylene-diamine, 10.75 grams (0.072 mole) of gamma What is claimed is: 1. A composition for dyeing animal ?bres which com prises an alkaline solution of a nitro phenylenediamine diethyl-amino-chloro-propane, and 80 cc. of water is 50 compound selected from the group consisting of 2-nitro heated by re?uxing for 2 hours. 1,4-phenylenediamine and 4-nitro-1,2-phenylenediamine The mixture is cooled and the nitroparaphenylene in which the amino group furthest from the nitro group is diamine which has not reacted is ?ltered. The ?ltrate is a group having the formula made alkaline by adding an aqueous sodium hydroxide solution, and is then extracted with ether. After conventional treatment an oil is obtained which 55 is transformed into a hydrochloride by passing aqueous hydrochloric acid into a solution of this product in ethanol. There is thus obtained a yield of about 70% in which R1, R2, and R3 each represent a substance se lected from the group consisting of hydrogen atoms and alkyl radicals from 1 to 3 carbon atoms, m represents an integer from 2 to 4 and n is equal to 0 or 1. of the dichlorhydride of 1-N(gamma-diethyl-amino 2. A method of dyeing animal ?bres which consists in 60 propyl) nitro-3-diamino-1,4-benzene which when recrys applying thereto an alkaline solution of a nitro phenylene tallized is absolute ethanol and melts with decomposition diamine compound selected from the group consisting of at 160° C. 2-nitro-1,4-phenylenediamine and 4-nitro-1,2-phenylene Analysis: diamine in which the amino group furthest from the 65 nitro group is a group having the formula Element Theory 46. 1 7. O8 16. 51 Found 45. 50-45. 43 7. 09-6. 93 15 78—16. 30 in which R1, R2 and R3 each represent a substance selected from the group consisting of hydrogen atoms and alkyl 70 radicals from 1 to 3 carbon atoms, m represents an integer from 2 to 4, and n is equal to 0 or 1. 3. A composition for dyeing animal ?bres which com prises an alkaline solution of 1-amino-2-nitro-4-(yo-amino ethyl) amino benzene. applied cold to white hair and left in contact therewith 75 4. A composition for dyeing animal ?bres which com for 15 minutes and produces a violine red shade. An aqueous 1% solution of the hydrochloride of said composition, brought to pH 7 by adding ammonia, is 3,049,393 10 prises an alkaline solution of 1-nitr0-3-amino-4-(?-amino~ ethyl) amino benzene. - prises an ‘alkaline solution of 1-N(g-amma-diethylamino~ propyl) nitro-3-diamino-1,4-benzene. 11. A composition for dyeing animal ?bres which com 5. A composition for dyeing animal ?bres which com prises an alkaline ‘solution of 1—N[(beta-diethylamino prises an alkaline solution of l-amino-2-nitro-4-(N-acet 5 ethyl) (ethyl)] nitro-3-diamino-1,4-benzener amido)~amino benzene. 6. A composition for dyeing animal ?bres whichycom References Cited in the ?le of this patent prises an alkaline solution of _1-N\(beta-diethylamino UNITED STATES PATENTS ethyl) nitro-3-diamino-1,4-benzene. 7. A composition for dyeing animal ?bres which com 1,932,901 Lehmann _____________ __ Oct. 31, 1933 prises an alkaline solution of 1-N(beta-dimethylamino 10 2,618,657 Vaughn _____________ .._ Nov. 18, 1952 ethyl) nitro-3-diamino-1,4-benzene. 8. A composition for dyeing animal ?bres which com 2,750,326 Eckardt __r ____________ __ June 12, 1956 1,051,605 France _______________ __ Ian. 18, 1954 FOREIGN PATENTS prises an alkaline solution of 1-N[(beta-diethylamino ethyl) (methyl)] nitro-S-diamino-1,4-benzene. 9. A composition for dyeing animal ?bres which com 15 prises an alkaline solution of l-N(beta-diethylamino ethyl) nitro-4-cliamino-1,2-benzene. 10. A composition for dyeing animal ?bres which com 4 OTHER REFERENCES Weissberger: Abstract from 0.6., vol. 652, pp. 289-290, November 6, 1951.